JP2002037997A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition that has further enhanced flame-retardancy in the aromatic polycarbonate resin composition mainly including silicone as a flame retardant, in more detail, provide a flame-retardant aromatic polycarbonate resin composition that has good burn dripping inhibition in addition to excellent long-term properties, for example, thermal stability, moist heat resistance and the like. SOLUTION: The objective flame-retardant aromatic polycarbonate composition comprises 99.9-94.7 wt.% of aromatic polycarbonate resin (component a), 0.01-5 wt.% of silicone bearing Si-H bonds (component b) and 0.001-0.3 wt.% of at least one selected from radical initiator, organic alkali metal salt and organic alkaline earth metal salt (component c) wherein the total of the components amounts to 100 wt.% and the total of the components b and c is >=0.1 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a flame-retardant aromatic polycarbonate resin composition. More specifically, the present invention relates to a flame-retardant aromatic polycarbonate resin composition which is excellent in drip prevention performance of a resin during combustion and excellent in flame retardancy.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are formed into various molded products by a simple and excellent productivity processing method such as injection molding, and are used in a wide range of industrial fields. Also,
A flame-retardant aromatic polycarbonate resin composition obtained by adding a halogen-based compound or a phosphorus-based compound to an aromatic polycarbonate resin has been used for OA equipment, home electric appliances, and the like, for which there is a strong demand for flame retardancy. However, on the other hand, flame-retardant aromatic polycarbonate resin compositions replacing these flame retardants have been developed and are being used in the above-mentioned products and the like. The purpose of such a change in the flame retardant is to suppress the generation of corrosive gas during molding or to improve the recyclability of products.

[0003] As a flame retardant in place of the flame retardant mentioned above, for example, a silicone compound can be mentioned. In recent years, flame-retardant resin compositions in which a silicone compound is blended with an aromatic polycarbonate resin have been energetically studied, and various proposals have been made.

For example, a method of blending an alkali (earth) metal salt of perfluoroalkanesulfonic acid with an organic siloxane having an alkoxy group, a vinyl group and a phenyl group in a polycarbonate resin (Japanese Patent Laid-Open No. 6-306265); A method of blending an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid with an organopolysiloxane containing an organooxysilyl group bonded to a silicon atom through a divalent hydrocarbon group (Japanese Patent Laid-Open No. 6-336546) Gazette) has been proposed.

[0005] Further, a method of blending a silicone compound with a specific petroleum heavy oil or pitch in a resin component (JP-A-9-169914), and a method in which a non-silicone resin having an aromatic ring has the formula R ₂ SiO _1.0 Units and RS
It has a unit represented by iO _1.5 and has a weight average molecular weight of 1
A method of compounding a silicone resin having a molecular weight of from 000 to 270,000 (JP-A-10-139964)
And so on.

[0006] However, the polycarbonate resin composition proposed above does not have sufficient flame retardancy. For example, problems have arisen in that, for example, a thin wall causes a drip and cannot achieve the V-0 rank of UL standard 94, or a coloring agent or the like easily causes a drip and cannot achieve a V-0.

On the other hand, Japanese Patent Publication No. Sho 60-38419 specifically describes a resin composition comprising an aromatic polycarbonate resin, an organic alkali metal salt, and poly (methyl hydrogen siloxane). However, such resin compositions did not have sufficient long-term properties such as thermal stability and wet heat resistance.

Further, as an anti-drip agent, polytetrafluoroethylene having a fibril forming ability is often used at present. However, in some cases, polytetrafluoroethylene cannot be blended, and there has been a demand for a flame-retardant aromatic polycarbonate resin composition which mainly uses a silicone compound as flame retardant, and which has sufficient drip prevention performance.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin composition mainly containing a silicone compound as a flame retardant, and a flame retardant aromatic polycarbonate resin composition having further improved flame retardancy. To provide. More specifically, it is an object of the present invention to provide a flame-retardant aromatic polycarbonate resin having good anti-drip performance and also having excellent long-term properties such as heat stability and wet heat resistance.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that aromatic polycarbonate resins,
Flame-retardant aromatic polycarbonate intended by combining a specific amount of a silicone compound having a Si-H bond and at least one compound selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt The present inventors have found that a resin composition can be obtained, and have reached the present invention.

[0011]

The present invention provides an aromatic polycarbonate resin (component (a)) of 99.9 to 94.7% by weight,
Silicone compound containing Si-H bond (component b) 0.0
1 to 5% by weight, and at least one compound (component (c)) selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt, 0.001 to 0.3.
The present invention relates to a flame-retardant aromatic polycarbonate resin composition comprising 100% by weight in total, and the total amount of the component b and the component c is at least 0.1% by weight or more.

The aromatic polycarbonate resin used as the component (a) in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, and also comprises a carbonate prepolymer. Is obtained by polymerizing the compound by a solid phase transesterification method, or obtained by polymerizing the compound by a ring opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, a terminal stopper and an oxidation of the dihydric phenol are required. An antioxidant or the like for prevention may be used. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When the composition contains a polyfunctional compound capable of producing such a branched polycarbonate resin, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (6) can be shown.

[0021]

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(Wherein A is a hydrogen atom or a group having 1 to 9 carbon atoms)
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Other monofunctional phenols include:
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (7) and (8) as a substituent are preferably used.

[0024]

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[0025]

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(Wherein X is -RO-, -R-CO-O
— Or —RO—CO—, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. Show. )

As the substituted phenols of the general formula (7), those having n of 10 to 30, especially 10 to 26, are preferred. Specific examples thereof include decyl phenol, dodecyl phenol, tetradecyl phenol, hexadecyl phenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (8), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salts and potassium salts of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In order to reduce the number of phenolic terminal groups in such a polymerization reaction, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred,
Particularly, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. It is used at a rate of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, high-temperature properties and the like will be reduced, and if it exceeds 50,000, the moldability will be reduced. 10,00
It is preferably from 0 to 50,000, and from 14,000 to 3
000 is more preferable, and 1 is more preferable.
4,000 to 24,000. Also, two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

In particular, a mixture with a polycarbonate resin having a viscosity average molecular weight of more than 50,000 is preferable because it has a high drip preventing ability and more effectively exerts the effects of the present invention. More preferably, the viscosity average molecular weight is 80,
A mixture with 2,000 or more polycarbonate resins,
More preferably, it is a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more. GPC (gel permeation chromatography)
Those having a molecular weight distribution of two or more peaks by such a method can be preferably used.

The viscosity average molecular weight referred to in the present invention is determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution] The obtained specific viscosity is inserted by the following equation to obtain the viscosity average molecular weight M. Ask for. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The component (b) of the present invention is a silicone compound having a Si—H bond. As the silicone compound, various compounds can be used. More preferably, the silicone compound having a viscosity at 25 ° C. of 150 mm ² / sec or less represented by the following general formulas (1) and (2); It is at least one or more silicone compounds selected from the silane compounds shown in 4) and (5).

[0039]

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[0040]

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(In the formulas (1) and (2), Z ^{1 to} Z ⁶ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or the following general formula (3) Α1 to α6 each independently represent 0 or 1. R ^{1 to} R ⁴ each independently represent a monovalent organic residue having 1 to 20 carbon atoms, and m1 represents an integer of 0 or more. , M2 is 3
Represents the above integer. Furthermore, the compounds of the formulas (1) and (2) each have at least one or more Si—H bond, and in the formula (1), when m1 is 2 or more, the repeating units are different from each other. You can take units. The repeating unit in the formula (2) can take a plurality of different repeating units. )

[0042]

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(In the formula (3), Z ^{7 to} Z ⁹ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α
7 to α9 each independently represent 0 or 1. Also R ⁵
And R ⁶ each independently represent a monovalent organic residue having 1 to 20 carbon atoms. m3 represents an integer of 0 or more. Further, in formula (3), when m3 is 2 or more, the repeating unit can take a plurality of different repeating units. )

[0044]

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[0045]

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(In the formulas (4) and (5), Z ^{10 to} Z ¹⁹
Each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. α10 to α19 each independently represent 0 or 1. Y represents a divalent organic residue. Equation (4)
And the compound of formula (5) has at least one or more Si-H bonds. )

The above general formulas (1), (2), (4) and
R of (5)¹~ R⁶, And Z¹~ Z^{1 9}Carbon number in
Preferably an alkyl group as a monovalent organic residue of -20,
Vinyl group, cycloalkyl group, aryl group, aralkyl
Groups, and these groups further include a hydroxyl group and an epoxy group.
Xy group, carboxyl group, carboxylic anhydride group, amino
Groups and various functional groups such as mercapto groups
There may be. More preferably, alkyl having 1 to 8 carbon atoms
Group, a vinyl group or an aryl group,
4 is preferably an alkyl group, a vinyl group, or a phenyl group.
No.

In the above general formulas (1) to (3), when a plurality of repeating units of a siloxane bond are present, they can take any form of random copolymerization, block copolymerization and tapered copolymerization. It is. In the case of a mixture of a plurality of polysiloxanes having different repeating units, the values of m1 to m3 in the general formulas (1) to (3) represent their average values.

In the present invention, in the above formula, 1
Compounds having two or more Si-H bonds in the molecule are preferred. Having a plurality of Si—H bonds facilitates formation of a silicone structure during combustion. More preferably, it is a compound having three or more Si-H bonds in one molecule. . Here, the structure of silicone refers to a network structure formed by a reaction between silicone compounds or a reaction between a resin and silicone.

For the above reason, the silicone compound represented by the above general formula (1) or (2) is more preferable as the component (b) of the present invention.
This is the case with a -H bond. This is because when the polymer or oligomer is represented by the above general formula (1) or (2), it is considered that a large silicone structure is likely to be formed because the molecule is large. More preferred as the component b in the present invention is that all the repeating units in the above general formula (1) or (2) are Si
It is a case having an —H bond, and particularly preferred is a case where all the repeating units are methyl hydrogen siloxane units (that is, in the general formula (1), Z ³ is a hydrogen atom,
α3 is 0, Z ⁴ is a methyl group, and α4 is 0. Formula (2) Z ⁵ is a hydrogen atom, .alpha.5 is 0, Z ⁶ is a methyl group, and α6 is 0. ).

On the other hand, in order for the silicone compound (b) to efficiently exhibit a flame retardant effect, its dispersed state is important. This is because if the silicone compound is unevenly distributed, it becomes difficult to form a uniform silicone structure during combustion. An important factor that determines such a dispersion state is a molecular weight.

From this point of view, the component b of the present invention is more preferably a silicone compound represented by the general formula (1) or (2) and having a viscosity at 25 ° C. of 150 mm ² / sec or less. More preferably, the viscosity at 25 ° C. is 5 to 100 mm ² / sec,
More preferably, it is 10 to 80 mm ² / sec. In such a case, as the repeating units m1, m2, and m3 in the above formulas (1) to (3), the total of these repeating units is preferably 3 to 100, more preferably 5 to 80, and still more preferably 10 to 70. It is.

Specific examples of the silicone compound represented by the general formula (1) include methyl hydrogen polysiloxane and a methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer. Examples of the methyl hydrogen polysiloxane include SH1107 manufactured by Dow Corning Toray Silicone Co., Ltd., KF99 manufactured by Shin-Etsu Chemical Co., Ltd., and T manufactured by GE Toshiba Silicone Co., Ltd.
SF484, TSF483, etc., which are readily available on the market. Examples of methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer include SiH-modified silicone oil L-3 manufactured by Nippon Unicar Co., Ltd.
1, FZ-3702, FZ-3797, FZ-3805
And these are easily available on the market.

Other silicone compounds represented by the general formula (1) include pentamethyldisiloxane, 1,1,
1,3,5,5,5-heptamethyltrisiloxane, tris (trimethylsiloxy) silane, 1,1,3,3-
Tetramethyldisiloxane, 1,1,3,3,5,5-
Hexamethyltrisiloxane, 1,1,1,3,5
7,7,7-octamethyltetrasiloxane and the like can be mentioned.

Examples of the silicone compound represented by the general formula (2) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane and pentamethylcyclopentasiloxane. Examples include tetrasiloxane.

Specific examples of the silane compound represented by the general formula (4) used as the component b in the present invention include the following. Compounds having one Si-H bond in one molecule include dimethoxymethylsilane, trimethoxysilane, dimethylethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, diethylmethylsilane, triethylsilane, butyldimethylsilane,
Examples include triethoxysilane, dimethylphenylsilane, methylphenylvinylsilane, diphenylmethylsilane, tripropylsilane, tripentyloxysilane, triphenylsilane, and trihexylsilane. Compounds having two Si—H bonds in one molecule include diethylsilane, allyldimethylsilane,
Methylphenylsilane, diphenylsilane, and the like can be given. Furthermore, Si—H bonds are formed in 3 molecules in one molecule.
Examples of the compound having one include phenylsilane and octylsilane.

As the silane compound represented by the above general formula (5) used as the component b of the present invention, specifically,
4-bis (dimethylsilyl) benzene, and 1,1,
3.3-tetramethyldisiloxane and the like can be mentioned.

The above silane compounds may be used alone or in combination of two or more.

The radical generator used as the component c in the present invention includes 2,5-dimethyl-2,5-di (t-
Organic peroxides such as butylperoxy) hexine-3 and dicumyl peroxide; and 2,3-dimethyl-2,3-diphenylbutane (dicumyl). These are Perhexin 25B manufactured by NOF CORPORATION, PARK MILL D, Nofmer BC, and the like, and are easily available. Especially during melt kneading, the generation of radicals is as small as possible,
Since it is preferable to generate a stable radical to some extent effectively at the time of combustion, 2,3-dimethyl-2,3-diphenylbutane (dicumyl) can be mentioned as a more preferable radical generator.

As the organic alkali metal salt and organic alkaline earth metal salt used as the component c in the present invention, various metal salts conventionally used for making polycarbonate resins flame-retardant can be used. And especially metal salts of organic sulfonic acids or metal salts of sulfates. These can be used alone or in combination of two or more. Incidentally, as the alkali metal of the present invention, lithium, sodium, potassium, rubidium, cesium may be mentioned, and as the alkaline earth metal, beryllium, magnesium, calcium, strontium, barium may be mentioned, and particularly preferably lithium, sodium, Potassium.

The metal salts of the organic sulfonic acids of the present invention include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkali metal salts of aromatic sulfonic acids. Earth metal salts and the like. Preferred examples of such an aliphatic sulfonic acid metal salt include an alkali (earth) metal alkanesulfonate and an alkali sulfonic acid in which a part of the alkyl group of the alkali (earth) metal alkanesulfonate is substituted with a fluorine atom. (Earth) metal salts, and alkali (earth) metal salts of perfluoroalkanesulfonic acid, and these can be used alone or in combination of two or more. Classification) The term metal salt is used to mean both alkali metal salts and alkaline earth metal salts.

Preferred examples of the alkanesulfonic acid used for the alkali (earth) metal salt of the alkanesulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, Heptanesulfonic acid, octanesulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more. Further, a metal salt in which a part of such an alkyl group is substituted with a fluorine atom can also be mentioned.

On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid,
Perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. Is 1
To 8 are preferred. These can be used alone or in combination of two or more.

As such an alkali (earth) metal salt of an alkanesulfonic acid, sodium salt of ethanesulfonic acid is exemplified by an alkali (earth) of perfluoroalkanesulfonic acid.
As the metal salt, potassium perfluorobutanesulfonate can be preferably mentioned.

The aromatic sulfonic acid used in the alkali (earth) metal salt of an aromatic sulfonic acid includes monomeric or polymeric sulfonic acid of aromatic sulfide, sulfonic acid of aromatic carboxylic acid and ester, monomeric or sulfonic acid of ester. Polymeric aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic At least one acid selected from the group consisting of sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids by methylene-type bonds can be given, and these can be used alone or in combination of two or more. Can be used.

The alkali (earth) sulfonate metal salt of a monomeric or polymeric aromatic sulfide is described in JP-A-50-98539.
For example, disodium diphenylsulfide-4,4'-disulfonate, diphenylsulfide-4,4 '
-Dipotassium disulfonate.

The alkali (earth) metal salts of sulfonic acids of aromatic carboxylic acids and esters are described in JP-A-50-9.
No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

The alkali (earth) sulfonate metal salt of a monomeric or polymeric aromatic ether is described in JP-A-50-98542, for example, calcium 1-methoxynaphthalene-4-sulfonate. ,
Disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysodium sulfonate, poly (1,3-phenylene oxide) polysodium sulfonate, poly (1,1
4- (phenylene oxide) polysodium polysulfonate, poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-
Butylphenylene oxide) lithium polysulfonate and the like.

The alkali (earth) sulfonate metal salt of an aromatic sulfonate is described in JP-A-50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

The monomeric or polymeric alkali (earth) metal salts of aromatic sulfonates are disclosed in
No. 98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl-3,3′-disulfone Calcium acid and the like can be mentioned.

The monomeric or polymeric alkali (earth) metal salts of aromatic sulfone sulfonates are described in JP-A-52-54746, for example, sodium diphenylsulfon-3-sulfonate, diphenylsulfone Potassium-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfon-3,4'-disulfonate, and the like can be given.

The alkali (earth) metal sulfonate metal salt of an aromatic ketone is described in JP-A-50-98547. For example, sodium α, α, α-trifluoroacetophenone-4-sulfonate, Benzophenone-3,3'-dipotassium dipotassium and the like can be mentioned.

The heterocyclic sulfonate alkali (earth) metal salts are described in JP-A-50-116542. For example, disodium thiophene-2,5-disulfonate, thiophene-2,5- Dipotassium disulfonate, calcium thiophene-2,5-disulfonate,
Examples thereof include sodium benzothiophene sulfonate.

The alkali (earth) metal sulfonate of aromatic sulfoxide is described in JP-A-52-54545, and examples thereof include potassium diphenylsulfoxide-4-sulfonate. .

Examples of the condensate of an alkali metal salt of an aromatic sulfonate (earth) by a methylene type bond include a formalin condensate of sodium naphthalene sulfonate and a formalin condensate of sodium anthracene sulfonate.

On the other hand, examples of the alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monohydric and / or polyhydric alcohols. Or, as sulfates of polyhydric alcohols, methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkyl phenyl ether sulfate, pentaerythritol mono,
Examples thereof include di, tri, tetrasulfate, sulfate of monoglyceride laurate, sulfate of monoglyceride palmitate, and sulfate of monoglyceride stearate. Preferred examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides, such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonate. Imide, N-
(N'-benzylaminocarbonyl) sulfanylimide, and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanylimide.

Among the above-mentioned alkali (earth) metal salts, more preferable components include an alkali (earth) metal salt of aromatic sulfonic acid and an alkali (earth) metal salt of perfluoroalkanesulfonic acid. Can be.

Next, the composition ratio of each component will be described. The composition ratio of the aromatic polycarbonate resin used as the component a in the present invention is 10% in total of the components a to c.
It is 99.9 to 94.7% by weight in 0% by weight.

The composition ratio of the silicone compound containing a Si—H bond as the component b of the present invention is 0.01 to 5% by weight based on 100% by weight of the total of the components a to c. Preferably it is 0.1 to 3% by weight, more preferably 0.5 to 3% by weight.
% By weight. If the compounding ratio of the component b is less than 0.01% by weight, the flame retardancy is insufficient, and if it exceeds 5% by weight, the strength such as heat resistance and impact resistance is reduced.

The composition ratio of at least one compound selected from the radical generator, the organic alkali metal salt, and the organic alkaline earth metal salt, which is the component c, is 0.1% in 100% by weight of the total of the components a to d. 001 to 0.3% by weight, preferably 0.005 to 0.3% by weight, more preferably 0.005 to 0.1% by weight. When the compounding ratio of the component c is less than 0.001% by weight, the flame retardancy is insufficient. The drop is large.

It is necessary that the total amount of the components b and c is at least 0.1% by weight, more preferably 0.3% by weight, based on 100% by weight of the total of the components a to c. % Or more, particularly preferably 0.35% by weight
Not less than 3.1% by weight. When the total amount of the component b and the component c is less than 0.1% by weight, the flame retardancy becomes insufficient.

The flame-retardant aromatic polycarbonate resin composition of the present invention is itself excellent in drip prevention performance. However, an anti-drip agent can be further included as a d component for the purpose of further improving the anti-drip performance.

Examples of the anti-drip agent used as the component d in the present invention include fluorine-containing polymers having fibril-forming ability. Examples of such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, Tetrafluoroethylene / hexafluoropropylene copolymer, etc.), US Pat.
No. 910, a partially fluorinated polymer,
Polycarbonate resins produced from fluorinated diphenols can be mentioned, but polytetrafluoroethylene is preferable.

The polytetrafluoroethylene having a fibril-forming ability is a powder obtained by coagulating and drying a latex obtained by emulsion polymerization of tetrafluoroethylene (a so-called fine powder of polytetrafluoroethylene, which is classified into Type 3 in the ASTM standard). Classified). Alternatively, an aqueous dispersion (a so-called polytetrafluoroethylene dispersion) produced by adding a surfactant to the latex and concentrating and stabilizing the latex may be mentioned.

The molecular weight of the polytetrafluoroethylene having the ability to form fibrils is 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000, in terms of the number average molecular weight determined from the standard specific gravity.

The polytetrafluoroethylene having a fibril-forming ability has a primary particle diameter of 0.05 to
It is preferably in the range of 1.0 μm, more preferably 0.1 to 0.5 μm. When fine powder is used, the secondary particle diameter can be 1 to 1000 μm, and more preferably 10 to 500 μm.

Such polytetrafluoroethylene is UL
Polytetrafluoroethylene having a fibril-forming ability and having a fibril-forming ability in a standard vertical combustion test has a drip-preventing performance at the time of a combustion test of a test piece. For example, Mitsui-DuPont Fluorochemical Co., Ltd.
Teflon (registered trademark) 6J and Teflon 30J,
Polykin MPA FA- made by Daikin Chemical Industry Co., Ltd.
500, Polyflon F-201L and Polyflon D-
1 and CD076 manufactured by Asahi IC Fluoropolymers Co., Ltd.

As such polytetrafluoroethylene, a fine powder which has been subjected to various treatments in order to prevent secondary agglomeration is more preferably used. As such a treatment, the surface of polytetrafluoroethylene may be calcined. In addition, as such a treatment, the surface of polytetrafluoroethylene having a fibril-forming ability may be coated with polytetrafluorotetrafluoroethylene having a non-fibril-forming ability.
More preferred in the present invention is polytetrafluoroethylene subjected to the latter treatment. In the former case, the intended fibril-forming ability tends to decrease. In such a case, the content of polytetrafluoroethylene having a fibril-forming ability is preferably in the range of 70 to 95% by weight of the total amount. The non-fibril-forming polytetrafluoroethylene has a molecular weight of 10,000 to 1,000,000, more preferably 1 to 10,000 in number average molecular weight determined from the standard specific gravity.
10,000 to 800,000.

As the polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), not only a solid form as described above, but also an aqueous dispersion form can be used. Further, PTFE having such fibril-forming ability can use a PTFE mixture of the following forms in order to improve the dispersibility in a resin and to obtain better flame retardancy and mechanical properties.

First, a coagulated mixture of a PTFE dispersion and a dispersion of a vinyl polymer can be given. Specifically, JP-A-60-258263 discloses an average particle size of 0.0
A method is described in which a PTFE dispersion of 5 to 5 μm is mixed with a dispersion of a vinyl polymer, PTFE particles larger than 30 μm are coagulated without purification, and the coagulated product is dried to obtain a PTFE mixture. The use of such mixtures is possible.

Secondly, a mixture obtained by mixing a PTFE dispersion and dried polymer particles can be mentioned. As such polymer particles, various types can be used, and more preferably, polycarbonate resin powder or ABS resin powder is used. It was done. For such a mixture, JP-A-4-272957 discloses a PTFE dispersion and ABS.
A mixture with a resin powder is described, and such a method can be used.

Thirdly, a PTFE mixture obtained by simultaneously removing each medium from a mixture of a PTFE dispersion and a thermoplastic resin solution can be mentioned. Specifically, the medium is obtained by using a spray drier. The removed mixture can be mentioned, and such a mixture is described in JP-A-08-188653.

Fourthly, a PTFE mixture obtained by polymerizing another vinyl monomer in a PTFE dispersion can be mentioned.
Japanese Patent No. 5583 specifically describes a method for obtaining a PTFE mixture by supplying styrene and acrylonitrile into a PTFE latex, and such a mixture can be used.

Fifth, a method of mixing a PTFE dispersion and a polymer particle dispersion and then polymerizing a vinyl monomer in the mixed dispersion can be mentioned. Can be cited as a preferred PTFE mixture in terms of achieving both fine dispersion. The details of such a mixture are described in JP-A-11-29679, that is, a particle size of 0.05 to 1.0 μm.
In a dispersion obtained by mixing a m-PTFE dispersion and a polymer particle dispersion, a monomer having an ethylenically unsaturated bond is emulsion-polymerized, and then a PTFE mixture pulverized by coagulation or spray drying is preferable. It can be mentioned as.

Here, the polymer particles include a block copolymer composed of polypropylene, polyethylene, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, ASA resin, polyalkyl (meth) acrylate, styrene and butadiene. The hydrogenated copolymer, a block copolymer composed of styrene and isoprene, and the hydrogenated copolymer, an acrylonitrile-butadiene copolymer, a random copolymer and a block copolymer of ethylene-propylene, and a copolymer of ethylene-butene Random copolymer and block copolymer, copolymer of ethylene and α-olefin, copolymer of ethylene-unsaturated carboxylic acid ester such as ethylene-butyl acrylate, acrylate-butadiene copolymer, polyorgano Shiroki Rubber and a copolymer obtained by grafting a vinyl-based monomer such as styrene, acrylonitrile, or polyalkyl methacrylate onto such a composite rubber. (Meth) acrylate, polystyrene, AS resin, ABS resin and ASA resin are preferred.

On the other hand, monomers having an ethylenically unsaturated bond include styrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene and α-methylstyrene. Styrene monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid-2-
Ethylhexyl, 2-ethylhexyl methacrylate,
Acrylic ester monomers such as dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. can do. These monomers can be used alone or in combination of two or more.

As the PTFE mixture of the fifth embodiment, METABLEN “A3000” is available from Mitsubishi Rayon Co., Ltd.
(Trade name) is commercially available, easily available, and can be preferably used in the present invention.

The ratio of PTFE in the PTFE mixture was 1% by weight in 100% by weight of the PTFE mixture.
-60% by weight, more preferably 3-40% by weight, even more preferably 5-30% by weight. When the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved.

The proportion of the drip inhibitor of the component d is as follows:
The amount is preferably 0.05 to 1 part by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of the total of the components a to c.
To 0.7 part by weight, particularly preferably 0.1 to 0.5 part by weight.

In the present invention, a char-forming compound can be added for the purpose of further improving the flame retardancy.
The char forming compounds include the following.

First, condensates of formaldehyde with a hydroxybenzene compound, a hydroxynaphthalene compound, a hydroxyanthracene compound, and the like can be given. For example, a novolak-type phenol resin and a cresol-modified phenol resin can be mentioned. Compounds having a sulfonic acid group or a sulfonic acid group are easily available and can be preferably used. For example, a formaldehyde condensate of sodium naphthalene sulfonate can be mentioned.

Secondly, condensates of heavy oils or pitches with formaldehyde can be mentioned. Such heavy oils or pitches have an aromatic hydrocarbon fraction fa value of 0.40 to 0.40.
0.95, and the aromatic ring hydrogen content Ha value is preferably 20 to 80%. For example, a condensate of paraformaldehyde and a bottom oil obtained in a fluid catalytic cracking step of vacuum gas oil can be mentioned.

Thirdly, the heavy oils or pitches themselves can be mentioned. Fourth, as thermoplastic resin types, poly (2,6-dimethyl-1,4-phenylene ether) and allylated poly (2,6-dimethyl-
1,4-phenylene ether), 2,6-diphenyl polyphenylene ether, polyparaphenylene, polyether sulfone, polyarylate, polyphenylene sulfide, polysulfone, polyether sulfone, and the like. Other examples include polyparaphenylene oligomers and 1,1′-thiobis (2-naphthol).

One selected from these or a combination of two or more can be used. Among these, particularly preferred char-forming resins include novolak-type phenol resins, poly (2,6-dimethyl-1,4-phenylene ether), and polyphenylene sulfide.

The ratio of the char forming compound is preferably 0.0 to 100 parts by weight of the total of the components a to c.
It is preferably 5 to 30 parts by weight, more preferably 0.1 to 2 parts by weight.
0 parts by weight, particularly preferably 0.1 to 5 parts by weight.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain various thermoplastic resins and additives as long as the effects of the present invention are exhibited.

The thermoplastic resin other than the polycarbonate resin includes, for example, polyethylene resin, polypropylene resin, polystyrene resin, MS resin, ABS resin,
AS resin, AES resin, ASA resin, SMA resin, poly-4-methylpentene-1, phenoxy resin, acrylic resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, polyamide resin, cyclic polyolefin resin, hydrogenated polystyrene Resins, polyarylate resins (amorphous polyarylate, liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, polyphenylenesulfide, and the like can be given. Further, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used.

Other various additives include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon,
Milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber,
Metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica,
Ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc., flame retardants (halogens, phosphate esters, metal salts, red phosphorus, metal hydrates) System), heat stabilizers, UV absorbers, light stabilizers,
Release agents, lubricants, sliding agents (such as PTFE particles), colorants (pigments and dyes such as carbon black and titanium oxide),
Light diffusing agents (crosslinked acrylic particles, crosslinked silicon particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, luminous pigments, fluorescent dyes, antistatic agents, flow modifiers, nucleating agents, inorganic and organic Antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers represented by graft rubber, infrared absorbers, and photochromic agents.

The flame-retardant aromatic polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer as a heat stabilizer. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various phosphite stabilizers can be used in the present invention. Specifically, for example, the general formula (9)

[0112]

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[Wherein R ⁸ is hydrogen or C 1-20]
An alkyl group, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio (the alkyl group has 1 to 3 carbon atoms)
0) or a hydroxy substituent, and the three R ^{8 s} can be selected whether they are the same or different from each other,
Further, a cyclic structure can be selected by being derived from a dihydric phenol. ] It is a phosphite compound represented by these.

Further, the general formula (10)

[0115]

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Wherein R ⁹ and R ¹⁰ are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, 20 cycloalkyl groups, having 15 to 15 carbon atoms
And represents 25 2- (4-oxyphenyl) propyl-substituted aryl groups. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. And a phosphite compound represented by the following formula:

Further, the general formula (11)

[0118]

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[Wherein R ¹¹ and R ¹² are alkyl groups having 12 to 15 carbon atoms. Note that R ¹¹ and R ¹² may be the same or different from each other. And a phosphite compound represented by the following formula:

Examples of the phosphonite stabilizer include a phosphonite compound represented by the following general formula (12) and a phosphonite compound represented by the following general formula (13).

[0121]

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[0122]

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[Wherein, Ar ¹ and Ar ^{2 each} represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or
It represents 5 to 25 2- (4-oxyphenyl) propyl-substituted aryl groups, and the four Ar ^{1 s} can be the same or different. Alternatively, ^two Ar ² may be the same or different. ]

Preferred specific examples of the phosphite compound corresponding to the general formula (9) include diphenylisooctyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Examples include diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, and phenyl di (tridecyl) phosphite.

Preferred specific examples of the phosphite compound corresponding to the above general formula (10) include distearylpentaerythritol diphosphite, bis (2,4
-Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite Phosphite and the like, preferably distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter
(tert-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds can be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the above general formula (11) include 4,4'-
Isopropylidene diphenol tetratridecyl phosphite.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (12) include tetrakis (2,4-di-iso-propylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di- tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylenediphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 ′
-Biphenylenediphosphonite; tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred; tetrakis (2,4-di-t
(tert-butylphenyl) -biphenylenediphosphonite is more preferred. This tetrakis (2,4-di-te
(rt-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylenediphosphonite (E2-1 component),
Tetrakis (2,4-di-tert-butylphenyl)
One kind of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more of them can be used in combination, but a mixture of these three is preferred. In the case of three kinds of mixtures, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the general formula (13) include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-diphenyl). -N-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-te)
rt-butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3 -Phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite and the like, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te
(rt-butylphenyl) -phenyl-phenylphosphonite is more preferred. This screw (2,4-di-tert)
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2 , 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite may be used alone or in combination, and preferably a mixture of the two. In the case of two kinds of mixtures, the mixing ratio is 5: 1 by weight.
-4 is preferable, and 5: 2-3 is more preferable.

On the other hand, examples of the phosphate-based stabilizers include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tribubutoxyethyl phosphate, and the like. Examples thereof include dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred is trimethyl phosphate.

More preferable phosphorus stabilizers for the above phosphorus stabilizers include compounds represented by the following formulas (14) and (15).

[0131]

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(In the formula (14), R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

[0133]

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(In the formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ ,
R ¹⁸ , R ²¹ , R ²² and R ²³ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ¹⁹ represents a hydrogen atom or a 1 to 1 carbon atom. 4 represents an alkyl group, and R ²⁰
Represents a hydrogen atom or a methyl group. )

In the formula (14), preferably, R ¹³ and R ¹⁴
Is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Equation (14)
Specific examples of the compound of (1) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, and tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-t
tert-butylphenyl) phosphite and the like, and particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

On the other hand, the phosphorus compound of the formula (15) can be produced by a known method. For example, a bisphenol compound represented by the following general formula (16) is reacted with phosphorus trichloride to obtain a corresponding phosphoric acid chloride, and thereafter, is reacted with the following general formula (1)
7) a method of reacting a phenol represented by the formula (17), and a reaction of the phenol represented by the formula (17) with phosphorus trichloride to produce a corresponding monoaryl phosphite dichloride, and further a bisphenol compound represented by the formula (16) And the reaction.

[0137]

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(In the formula (16), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group; ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁰ represents a hydrogen atom or a methyl group.)

[0139]

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(In the formula (17), R ²¹ , R ²² and R ²³
Represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, respectively. )

Specific examples of the compound represented by the general formula (16) include 2,2′-methylenebisphenol and 2,2′-
Methylenebis (4-methylphenol), 2,2′-methylenebis (6-methylphenol), 2,2′-methylenebis (4,6-dimethylphenol), 2,2′-
Ethylidenebisphenol, 2,2′-ethylidenebis (4-methylphenol), 2,2′-isopropylidenebisphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4,6-di-ter
t-butylphenol), 2,2′-methylenebis (4
-Methyl-6-cyclohexylphenol), 2,2 ′
-Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethylphenylmethane, 2,2 '
-Methylenebis (6-α-methyl-benzyl-p-cresol), 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol) and 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol) and the like, and they can be preferably used.

The compound of the general formula (16) is more preferably 2,2'-methylenebis (4-methyl-6-te
rt-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
2,2′-methylenebis (4,6-di-tert-butylphenol), 2,2′-ethylidene-bis (4,6
-Di-tert-butylphenol), and 2,2 '
-Butylidene-bis (4-methyl-6-tert-butylphenol).

On the other hand, specific examples of the compound of the general formula (17) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, −te
rt-butyl-4-methylphenol, 2,4-di-t
tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-
Methylphenol, 2,4-dimethyl-6-tert-
Butylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, 2,4,6-tri-tert-butylphenol, and 2,6-di-tert-butyl-4-s-butylphenol, and the like can be preferably used. A more preferable example of the compound of the general formula (17) is a case having two or more alkyl substituents.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a phenolic antioxidant. The phenolic antioxidant suppresses discoloration during heat exposure, and also exhibits some effect in improving flame retardancy. Various phenolic antioxidants can be used.

Specific examples of such phenolic antioxidants include, for example, vitamin E, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-
6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert)
-Butylphenol), 2,2'-methylenebis (4-
Methyl-6-cyclohexylphenol), 2,2′-
Dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis (4,6-di-
tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t
tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-
Hexanediol bis [3- (3,5-di-tert-
Butyl-4-hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl 6- (3-te
rt-butyl-5-methyl-2-hydroxybenzyl)
Phenyl] terephthalate, 3,9-bis {2- [3-
(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4 '-Thiobis (6-te
rt-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol),
2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6- Di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-butyl-4-hydroxyhydrocinnamide), N,
N'-bis [3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyl] hydrazine,
1,1,3-tris (2-methyl-4-hydroxy-5
-Tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-ter
t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like, It can be used preferably.

More preferably, n-octadecyl-β-
(4'-hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,
10-tetraoxaspiro [5,5] undecane and tetrakis [methylene-3- (3 ′, 5′-di-te
rt-butyl-4-hydroxyphenyl) propionate] methane, and furthermore n-octadecyl-β- (4 ′
-Hydroxy-3 ', 5'-di-tert-butylfell) propionate is preferred.

The flame-retardant aromatic polycarbonate resin composition of the present invention can contain a sulfur-based antioxidant. It is particularly suitable when the molding is performed by rotational molding or compression molding. Specific examples of such sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate. , Distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra (β-
Laurylthiopropionate) ester, bis [2-methyl-4- (3-laurylthiopropionyloxy)-
5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2
-Mercapto-6-methylbenzimidazole, 1,
1'-thiobis (2-naphthol) and the like can be mentioned. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The above-mentioned phosphorus-based stabilizers, phenol-based antioxidants and sulfur-based antioxidants can be used alone or in combination of two or more. The case where a phosphorus-based stabilizer is essential is more preferable, and it is particularly preferable that the compound of the general formula (14) is contained as the phosphorus-based stabilizer.

The proportion of these stabilizers in the composition is as follows: per 100 parts by weight of the flame-retardant aromatic polycarbonate resin composition of the present invention, phosphorus-based stabilizer, phenol-based antioxidant, or sulfur-based antioxidant Is 0.00
It is preferably from 01 to 1 part by weight. More preferably, the amount is 0.0005 to 0.5 part by weight per 100 parts by weight of the flame-retardant aromatic polycarbonate resin composition. More preferably, it is 0.001 to 0.2 parts by weight.

The flame-retardant aromatic polycarbonate resin composition of the present invention has good releasability, but may further contain a release agent if necessary. Since the present invention has good flame retardancy, good flame retardancy can be achieved even when a release agent that usually has a bad influence on flame retardancy is added. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin-based waxes (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compounds (the present invention) B
Other than ingredients. For example, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil and the like can be mentioned. Those modified with a functional group-containing compound such as acid modification can also be used), fluorine compounds (such as fluorine oil typified by polyfluoroalkyl ether), paraffin wax, and beeswax. Among them, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil and polymethylphenyl silicone oil, and fluorine oil can be mentioned. Such a release agent comprises components a to c
The amount is preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the total components.

Preferred release agents include saturated fatty acid esters, for example, monoglycerides such as stearic acid monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, and stearic acid stearates. Lower fatty acid esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used.

Since the flame-retardant aromatic polycarbonate resin composition of the present invention is often used for the housing of OA equipment and the like, it preferably contains an ultraviolet absorber. Examples of ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy -4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxy-5
Benzophenone-based ultraviolet absorbers represented by sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane and the like can be mentioned.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- [2′-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-te)
rt-butylphenyl) -5-chlorobenzotriazole, 2,2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
Benzotriazole ultraviolet absorbers represented by condensates with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol can be mentioned.

Further, as the ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate,
Condensate of 2,3,4-butanecarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid with 1,2,2 Condensation product of 6,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6
6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,
Condensation product with 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-tetraoxaspiro [5,5]
A condensate with undecane) diethanol and a hindered amine-based light stabilizer represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be blended.

The ratio of the ultraviolet absorber and the light stabilizer is as follows:
0.01 to 5 per 100 parts by weight of the total of the components a to c
Parts by weight, more preferably 0.02 parts by weight.
１1 part by weight.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a bluing agent in order to cancel a yellowish color due to an ultraviolet absorber or the like. As the bluing agent, any one can be used without any particular difficulty as long as it is used for a polycarbonate resin. Generally, anthraquinone dyes are easily available and preferred. Specific blueing agents include, for example, SolventViolet13 [CA. No
(Color Index No.) 60725; Trade name "Macrolex Violet B" manufactured by Bayer, "Diaresin Blue G" manufactured by Mitsubishi Chemical Corporation, "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd.], generic name S
solvent Violet 31 [CA. No.6821
0; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent Violet 33
[CA. No. 60725; Trade name "Diaresin Blue J" manufactured by Mitsubishi Chemical Corporation], generic name Solvent
Blue 94 [CA. No. 61500; Trade name “Diaresin Blue N” manufactured by Mitsubishi Chemical Corporation], generic name Sol
vent Violet 36 [CA. No. 68210;
Trade name Bayer Corporation “Macrolex Violet 3
R "], generic name Solvent Blue 97 [trade name" Macrolex Blue RR "manufactured by Bayer AG] and generic name Solvent Blue 45 [CA. No611
10; Trade name “TERAZOL BLUE RL” manufactured by Sando Co., Ltd.
S ”], Ciba Specialty Chemicals, Inc., Macrolex Violet, Terazol Blue RLS, and the like. Particularly preferred are Macrolex Blue RR, Macrolex Violet B, and Terazol Blue RLS.

For producing the flame-retardant aromatic polycarbonate resin composition of the present invention, any method is employed. For example, components a to c and optionally other components
After thoroughly mixing using pre-mixing means such as a mold blender, Henschel mixer, mechanochemical device, and extrusion mixer, granulation is optionally performed using an extrusion granulator or briquetting machine, and then a vented twin screw Examples thereof include a method of melting and kneading with a melt kneading machine represented by a ruder and a method of pelletizing with a device such as a pelletizer.

In addition, a method in which the components a to c and optionally other components are independently supplied to a melt kneader typified by a vented twin-screw ruder, a part of the components a to c is premixed. After that, a method of supplying the remaining components independently to the melt kneader, after diluting and mixing the components b and c with water or an organic solvent, supplying the melt kneader or premixing the diluted mixture with other components Thereafter, a method of supplying the mixture to a melt kneader may also be used. Further, when a dispersion component is used as the d component, it is also appropriate to adopt a method of mixing the d component and the c component. In addition, when there is a liquid component to be blended, a so-called liquid injection device or liquid addition device can be used for supply to the melt kneader.

The flame-retardant polycarbonate resin composition of the present invention can be used to produce various products by injection-molding such pellets to obtain molded products. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerless can be manufactured. In addition, in the injection molding, not only a normal molding method but also gas assist injection molding, injection compression molding, ultra-high speed injection molding and the like can be used.

The flame-retardant aromatic polycarbonate resin composition of the present invention can be obtained by extrusion molding of various shaped extruded products,
It can be used in the form of a sheet, a film and the like. For sheet and film molding, the inflation method,
A casting method or the like can also be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the flame-retardant aromatic polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading.

The flame-retardant aromatic polycarbonate resin composition of the present invention is excellent in thin-walled flame retardancy, and is also excellent in impact resistance and wet heat resistance, so that it is suitable for internal parts and housings of OA equipment and home electric appliances. It is something. Such applications include, for example, a relay case, a coil bobbin, an optical pickup chassis, a motor case, a notebook computer housing and internal parts, a CRT display housing and internal parts, a printer housing and internal parts, a mobile terminal housing and internal parts, a recording medium (CD, DVD,
(PD, FDD, etc.) Drive / housing and internal parts, copy machine housing / internal parts, electric / electronic parts typified by parabolic antennas and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser disc (registered trademark) / compact discs, lighting parts, refrigerator parts, air conditioner parts, Home and office electrical product parts such as typewriter parts and word processor parts. Vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrumental panels, center console panels, deflector parts, car navigation covers, car navigation parts, car stereo parts, and the like can also be mentioned. It is also useful for various uses such as machine parts and miscellaneous goods.

[0163]

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated. (1) Material properties (1-) Flame retardancy 1.6 mm and 1.5 mm in thickness prepared according to UL standard
The test was performed using a mm test piece. Based on the result of the test, it was evaluated as one of the ranks V-0, V-1 and V-2 in the UL standard 94. (1-) Thermal Stability During molding, the resin was kept at a cylinder temperature of 290 ° C. for 15 minutes, and the appearance of the molded product was evaluated by the following method to evaluate the thermal stability of the material. ：: No appearance defect such as silver occurred x: Appearance defect occurred such as silver

[Examples 1 to 16 and Comparative Examples 1 to 6]
The resin compositions described in Tables 1 to 3 were prepared in the following manner.
The description will be made according to the symbols in the following table.

First, the component c and 10 times its amount of PC-1 were uniformly mixed using a supermixer to prepare a master agent for the component c. The master agent of the component c and the remaining components were weighed at the ratios shown in Tables 1 to 3 and uniformly mixed using a tumbler, and the mixture was charged into an extruder to prepare a resin composition.

As the extruder, a vent type twin screw extruder having a diameter of 30 mmφ (KTX-30, Kobe Steel Ltd.) was used. The screw configuration includes the kneading zone of the first stage (consisting of kneading disk for feeding x2, rotor x1 for feeding, rotor x1 for returning, and x1 for returning kneading disk) before the vent position. Thereafter, the kneading zone of the second stage (rotor x
1 and a return rotor x 1). Cylinder temperature and die temperature of 280
The strand was extruded under the conditions of ℃ and vent suction degree of 3000 Pa, cooled in a water bath, and then cut with a pelletizer to form pellets.

The obtained pellets were dried at 110 ° C. for 5 hours by a hot air circulating drier, and the cylinder temperature was set to 290 ° C. by an injection molding machine [Fanac T-150D].
A test piece was formed at a mold temperature of 70 ° C.

The raw materials and the like used in Tables 1 to 3 are as follows. (A component) PC-1: linear polycarbonate resin (bisphenol A prepared by the phosgene method and p as a terminal stopper)
-A polycarbonate resin comprising tert-butylphenol. Such a polycarbonate resin was produced without using an amine-based catalyst, and the proportion of terminal hydroxyl groups in the terminal of the polycarbonate resin was 10 mol% and its viscosity average molecular weight was 22,500.) PC-2: Branched aromatic Group polycarbonate resin (Teflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.)

[0169] (b component) Si-1: viscosity at 25 ° C. of 20 mm ² / sec methylhydrogenpolysiloxane (Shin-Etsu Chemical Co., Ltd. KF99) Si-2: 25 Viscosity at ° C. of 20 mm ² / sec Methyl hydrogen polysiloxane-dimethyl polysiloxane copolymer (Silicone Oil L-31 manufactured by Nippon Unicar Co., Ltd.) (other than the component b) Si-3: A Si-H bond having a viscosity of 20 mm ² / sec at 25 ° C. Organic siloxane compound not containing (KF69 manufactured by Shin-Etsu Chemical Co., Ltd.) Si-4: The viscosity at 25 ° C. is 16.4 mm ² / sec.
Organosiloxane compound containing no Si-H bond of c (KR-219 manufactured by Shin-Etsu Chemical Co., Ltd.)

(Component c) Radical: 2,3-dimethyl-2,3-diphenylbutane (dicumyl) (NOFMER BC manufactured by NOF CORPORATION) Metal salt 1: potassium perfluorobutanesulfonate (Dainippon Ink & Chemicals, Inc.) MegaFac F-1
14P) Metal salt 2: potassium diphenylsulfonate (KSS manufactured by UCB Japan)

(Other Components) S-1: Phosphite antioxidant (IRGAFOS168 manufactured by Ciba-Geigy Japan) S-2: Phosphonite antioxidant (Sando)
z) Sandstab P-EPQ)

[0172]

[Table 1]

[0173]

[Table 2]

[0174]

[Table 3]

The following is clear from these tables. From the comparison between Examples 1 to 3 and Comparative Example 2, the S
It can be seen that the aromatic polycarbonate resin composition obtained using the silicone compound having an iH bond satisfies good flame retardancy. Also, from Example 2 and the like, it can be seen that good flame retardancy is achieved by adding the component b and the component c together. Examples 2 and 6
In the sample (1), a molded product of a keyboard frame of a notebook personal computer was molded from the sample. All of the molded products had sufficient strength, and particularly the strength of the weld portion was good.

[0176]

As is clear from the above, the flame-retardant aromatic polycarbonate resin composition of the present invention mainly contains a silicone compound as a flame retardant, has good anti-drip performance, and has a high heat stability. Also, it has excellent long-term properties such as heat and moisture resistance. Such properties are not present in conventional flame-retardant aromatic polycarbonate resins, and such resin compositions are excellent in flame retardancy in thin-walled molded articles and have high thermal stability even when melted at high temperatures such as injection molding. Has both. Therefore, it is extremely useful for various industrial uses such as the OA equipment field and the electric / electronic equipment field, and the industrial effect achieved is extremely large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/541 (C08L 69/00 // (C08L 69/00 83:05) 83:05) C08K 5 / 54

Claims (2)

[Claims] 1. An aromatic polycarbonate resin (a component)
99.9 to 94.7% by weight, selected from a silicone compound containing Si-H bond (component b) 0.01 to 5% by weight, a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt. Flame-retardant aromatic polycarbonate comprising at least one compound (component (c)) in a total amount of 0.001 to 0.3% by weight and a total amount of component (b) and component (c) of at least 0.1% by weight Resin composition. 2. The b component is represented by the following general formulas (1) and (2):
The viscosity at 25 ° C. is 150 mm ² / sec
The flame-retardant aromatic polycarbonate resin composition according to claim 1, which is at least one silicone compound selected from the following silicone compounds and silane compounds represented by the following general formulas (4) and (5). Embedded image Embedded image (In the formulas (1) and (2), Z ^{1 to} Z ⁶ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (3). Α1 to α6
Represents 0 or 1 each independently. R ^{1 to} R ⁴ each independently represent a monovalent organic residue having 1 to 20 carbon atoms.
m1 represents an integer of 0 or more, and m2 represents an integer of 3 or more. Furthermore, the compounds of the formulas (1) and (2) each have at least one or more Si—H bond, and in the formula (1), when m1 is 2 or more, the repeating units are different from each other. You can take units. The repeating unit in the formula (2) can take a plurality of different repeating units. ) (In the formula (3), Z ^{7 to} Z ⁹ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α7 to α9 each independently represent 0 or 1. R ⁵ And R ⁶ each independently represent a monovalent organic residue having 1 to 20 carbon atoms.
m3 represents an integer of 0 or more. Further, in formula (3), when m3 is 2 or more, the repeating unit can take a plurality of different repeating units. ) Embedded image (In the formulas (4) and (5), Z ^{10 to} Z ¹⁹ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α10 to α19 each independently represent 0 or 1. Y represents a divalent organic residue, and the compounds of the formulas (4) and (5) each have at least one or more Si-
Has an H bond. )